Physicochemical phenomena at the polymer-metal interface have been observed by the use of surface-enhanced Raman scattering (SERS). SERS spectra are compared with the infra-red reflection-absorption spectra for coatings of polymer on metals. Results show that SERS is an effective in situ analytical technique which is highly informative in that the authentic adsorption state and the microstructure of the first monolayer near the metal surface can be revealed with much less interference from the polymer bulk.